Composite tin and zinc oxide nanocrystalline particles for enhanced charge separation in sensitized degradation of dyes

Composite ZnO/SnO2 catalyst has been studied for the sensitized degradation of dyes e.g. Eosin Y (2', 4', 5', 7'-tetrabromofluorescein disodium salt) in relation to efficient charge separation properties of the catalyst. Improved photocatalytic activity was observed in the case of ZnO/SnO2 composite catalyst compared to the catalytic activity of ZnO, SnO2 or TiO2 powder. The suppression of charge recombination in the composite ZnO/SnO2 catalyst led to higher catalytic activity for the degradation of Eosin Y. Degradation of Eosin follows concomitant formation of CO2 and formation of CO2 followed a pseudo-first-order rate. Photoelectrochemical cells constructed using SnO2, ZnO, ZnO/SnO2 sensitized with Eosin Y showed V(oc) of 175, 306, 512 mV/cm2 and I(sc) of 50, 70, 200 microA/cm2 respectively. A higher irreversible degradation of Eosin Y and higher V(oc) observed on composite ZnO/SnO2 than ZnO and SnO2 separately can be considered as a proof of enhanced charge separation of ZnO/SnO2 catalyst. Eosin Y showed a higher emission decreases on ZnO/SnO2 composite than on individual ZnO, SnO2 or TiO2 indicating dominance of the charge injection process. Photoinjected electrons are tunneled from ZnO to SnO2 particles accumulating injected electrons in the conduction bands allowing wider separation of excited carriers.     

Degradation of ampicillin antibiotic in aqueous solution by ZnO/polyaniline nanocomposite as photocatalyst under sunlight irradiation

PURPOSE AND METHOD: ZnO/polyaniline nanocomposite in core-shell structure was prepared by the synthesis and adsorption of polyaniline chains on the structure of ZnO nanoparticles. Fourier transform infrared and ultraviolet-visible (UV-Vis) spectroscopy, X-ray diffraction patterns, field emission scanning electron microscopy, and transmission electron microscopy were used to characterize the composition and structure of the nanocomposite. The nanocomposite was used as an active photocatalyst for photodegradation and removal of ampicillin in aqueous solution. RESULTS: UV-Vis spectroscopy studies showed that ZnO/polyaniline nanocomposite absorbs visible light irradiation as well as ultraviolet spectrum, and therefore, it can be photoactivated under visible and ultraviolet lights. The photocatalytic activity of ZnO/polyaniline nanocomposite in degradation of ampicillin molecules in aqueous solution under natural sunlight irradiation was evaluated and compared with that of ZnO nanoparticles and pristine polyaniline. The ZnO/polyaniline core-shell nanocomposite exhibited higher photocatalytic activity compared to ZnO nanoparticles and pristine polyaniline. The effect of operating conditions (pH, ZnO/polyaniline nanocomposite dosage, and ampicillin concentration) in the photocatalytic degradation of ampicillin using ZnO/polyaniline nanocomposite was investigated. The optimum conditions for maximum efficiency of ampicillin degradation under 120 min sunlight irradiation were found as 10 mg L(-1) dosage of ZnO/polyaniline nanocomposite, ampicillin concentration of 4.5 mg L(-1), and solution pH?=?5. Under optimum operating conditions, degradation efficiency was reached to 41% after 120 min of exposure to the sunlight irradiation.     

Morphologies of zinc oxide particles and their effects on photocatalysis

ZnO powders with different morphologies were synthesized by alkali precipitation, organo-zinc hydrolysis, and spray pyrolysis. Acetaldehyde decomposition was used as a probe reaction to evaluate the photocatalysis of these ZnO powders. We investigated the relationship between photocatalytic activity and crystallinity, surface area, or morphology. Results indicate that the photocatalytic activity of ZnO powder depends on crystallinity rather than surface area for the same original ZnO powders prepared by equal conditions other than the difference in calcination temperature. However, no direct relationship between photocatalytic activity and crystallinity or surface area was found for the differently original ZnO powders prepared by different methods, or the same method with different conditions. Instead, we find that the particle morphology significantly affects its photocatalysis.     

Assessment of phytotoxicity of ZnO NPs on a medicinal plant, Fagopyrum esculentum

Fagopyrum esculentum commonly named as buckwheat plant is pseudocereal food crops and healthy herbs but is not known as a bioindicator of environmental condition. In the present study, the effects of ZnO nanoparticles (NPs) and microparticles (MPs) on plant growth, bioaccumulation, and antioxidative enzyme activity in buckwheat were estimated under hydroponic culture. The significant biomass reduction at concentrations of 10–2,000 mg/L was 7.7–26.4 % for the ZnO NP and 11.4–23.5 % for the ZnO MP treatment, (p?<?0.05). ZnO NPs were observed in root cells and root cell surface by scanning electron microscopy and transmission electron microscopy analysis. Zn bioaccumulation in plant increased with increasing treatment concentrations. The upward translocation (translocation factor <0.2) of Zn in plant was higher with the ZnO NP treatment than that with the ZnO MP treatment. Additionally, reactive oxygen species generation by ZnO NPs was estimated as the reduced glutathione level and catalase activity, which would be a predictive biomarker of nanotoxicity. The results are the first study to evaluate the phytotoxicity of ZnO NPs to medicinal plant. F. esculentum can be as a good indicator of plant species in NP-polluted environment.     

Ag/ZnO hollow sphere composites: reusable photocatalyst for photocatalytic degradation of 17α-ethinylestradiol

Characterizations of Ag/ZnO hollow sphere by scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectra, and UV–vis absorption spectra have been made after its synthesis. The results showed that the composite was hollow structure with diameters of about 1–4 μm. The samples synthesized were tested and identified as silver doped ZnO, which have extended and boosted the spectral absorption. The photocatalytic activity of Ag/ZnO hollow spheres was assessed using 17α-ethinylestradiol aqueous solution under UV irradiation. It has been observed that the 17α-ethinylestradiol absorption efficiency and degradation rate is higher for Ag/ZnO hollow spheres. As reusable photocatalysts, Ag/ZnO hollow spheres which could be easily separated from a suspension will facilitate their application in wastewater treatment with enhanced photostability.     

ZnO/LixNi1-xO光催化降解甲基橙的研究

采用溶胶凝胶法制备LixNi1-xO和ZnO粉体,利用球磨法制备ZnO/LixNi1-xO复合粉体,以紫外光为光源,通过降解甲基橙,研究了锂掺杂及n-p复合对氧化镍的光催化性能影响。结果表明：当投放量为0.1 g/L,x≤0.075（摩尔分数）的锂掺杂氧化镍均比未掺杂氧化镍的光催化活性高。当锂掺杂摩尔分数为0.025,投放量为0.4 g/L时锂掺杂氧化镍的光催化活性最佳,甲基橙最高降解率达到93.1%。当ZnO/Li0.025Ni0.975O在质量比为1∶1,投放量为0.2 g/L时光催化活性最佳,甲基橙最高降解率达到98.1%。     

H2O2 formation from photocatalytic processes at the ZnO/water interface

The paper focuses on the production of H2O2 by photocatalysis over ZnO in an aerated aqueous phase. The presence of different reductants that increase the H2O2 production in the aqueous phase is analysed; particular attention is paid to nitrite, which has been shown to be the reductant that produces the most significant increments in the H2O2 production. The photocatalytic anodic decomposition of ZnO in the presence of the different reductants is also investigated. From the results obtained, the relevance of the ZnO photocatalysis in the formation of environmental hydrogen peroxide is estimated.     

Cellular uptake and mutagenic potential of metal oxide nanoparticles in bacterial cells

Extensive production and consumption of nanomaterials such as ZnO and TiO₂ has increased their release and disposal into the environment. The accumulation of nanoparticles (NPs) in ecosystem is likely to pose threat to non-specific targets such as bacteria. The present study explored the effect of ZnO and TiO₂ NPs in a model bacterium, Salmonella typhimurium. The uptake of ZnO and TiO₂ bare NPs in nano range without agglomeration was observed in S. typhimurium. TEM analysis demonstrated the internalization and uniform distribution of NPs inside the cells. Flow cytometry data also demonstrates that both ZnO and TiO₂ NPs were significantly internalized in the S. typhimurium cells in a concentration dependent manner. A significant increase in uptake was observed in the S. typhimurium treated even with 8 and 80 ng mL⁻¹ of ZnO and TiO₂ NPs with S9 after 60 min, possibly the formation of micelles or protein coat facilitated entry of NPs. These NPs exhibited weak mutagenic potential in S. typhimurium strains TA98, TA1537 and Escherichia coli (WP2uvrA) of Ames test underscoring the possible carcinogenic potential similar to certain mutagenic chemicals. Our study reiterates the need for re-evaluating environmental toxicity of ZnO and TiO₂ NPs presumably considered safe in environment.     

Coupling of solar-assisted advanced oxidative and biological treatment for degradation of agro-residue-based soda bleaching effluent

This study evaluates the effect of integrated solar-assisted advanced oxidation process (AOP) and biological treatment on the extent of degradation of effluents from chlorination (C) and first alkaline extraction (E₁) stages of soda pulp bleaching in agro-residue-based pulp and paper mill. Biodegradation of the effluents was attempted in suspended mode using activated sludge from the functional pulp and paper industry effluent treatment plant acclimatized to effluents in question. The photocatalytic treatment was employed using zinc oxide (ZnO) in slurry mode for decontamination of effluents in a batch manner and the degradation was evaluated in terms of reduction in chemical oxygen demand. The biological treatment (24?h) of C and E₁ effluent resulted in 30 and 57?% of degradation, respectively. Solar-induced AOP of C and E₁ effluents resulted in 53 and 43?% degradation under optimized conditions (2.5?g?L^?1 ZnO at pH?8.0) after 6?h of exposure. For C effluent, a short duration of solar/ZnO (1?h) prior to biological treatment reduced the time required at biological step from 24 to 12?h for almost same extent (92?%) of degradation. However, sequential biological treatment (24?h) followed by solar/ZnO (2?h) resulted in 85.5?% degradation. In contrast, in the case of E₁ effluent, sequential biological (24?h)?Csolar/ZnO (2?h) system effectively degrades effluent to 95.4?% as compared to 84.8?% degradation achieved in solar/ZnO (2?h)?Cbiological treatment (24?h) system. In the present study, the sequencing of photocatalysis with the biological treatment is observably efficient and technically viable process for the complete mineralization of the effluents.     

Acute effects of Fe₂O₃, TiO₂, ZnO and CuO nanomaterials on Xenopus laevis

Metal oxide nanomaterials have exhibited toxicity to a variety of aquatic organisms, especially microbes and invertebrates. To date, few studies have evaluated the toxicity of metal oxide nanomaterials on aquatic vertebrates. Therefore, this study examined effects of ZnO, TiO₂, Fe₂O₃, and CuO nanomaterials (20-100 nm) on amphibians utilizing the Frog Embryo Teratogenesis Assay Xenopus (FETAX) protocol, a 96 h exposure with daily solution exchanges. Nanomaterials were dispersed in reconstituted moderately hard test medium. These exposures did not increase mortality in static renewal exposures containing up to 1000 mg L⁻¹ for TiO₂, Fe₂O₃, CuO, and ZnO, but did induce developmental abnormalities. Gastrointestinal, spinal, and other abnormalities were observed in CuO and ZnO nanomaterial exposures at concentrations as low as 3.16 mg L⁻¹ (ZnO). An EC₅₀ of 10.3 mg L⁻¹ ZnO was observed for total malformations. The minimum concentration to inhibit growth of tadpoles exposed to CuO or ZnO nanomaterials was 10 mg L⁻¹. The results indicate that select nanomaterials can negatively affect amphibians during development. Evaluation of nanomaterial exposure on vertebrate organisms are imperative to responsible production and introduction of nanomaterials in everyday products to ensure human and environmental safety.     

Chronic toxicity of ZnO nanoparticles, non-nano ZnO and ZnCl2 to Folsomia candida (Collembola) in relation to bioavailability in soil

The chronic toxicity of zinc oxide nanoparticles (ZnO-NP) to Folsomia candida was determined in natural soil. To unravel the contribution of particle size and free zinc to NP toxicity, non-nano ZnO and ZnCl₂ were also tested. Zinc concentrations in pore water increased with increasing soil concentrations, with Freundlich sorption constants K_f of 61.7, 106 and 96.4 l/kg (n = 1.50, 1.34 and 0.42) for ZnO-NP, non-nano ZnO and ZnCl₂ respectively. Survival of F. candida was not affected by ZnO-NP and non-nano ZnO at concentrations up to 6400 mg Zn/kg d.w. Reproduction was dose-dependently reduced with 28-d EC50s of 1964, 1591 and 298 mg Zn/kg d.w. for ZnO-NP, non-nano ZnO and ZnCl₂, respectively. The difference in EC50s based on measured pore water concentrations was small (7.94-16.8 mg Zn/l). We conclude that zinc ions released from NP determine the observed toxic effects rather than ZnO particle size.     

Heavy metal tolerance of rice plants (Oryza sativa L.) to some metal oxides at the critical levels

The toxicity of metal oxides (CdO, ZnO, PbO) were compared with each other and the critical levels of metal uptake by rice plants were determined. The order of metal toxicity to rice plants is CdO greater than ZnO greater than PbO. The highest concentration obtained for unpolished rice was 4.97 micrograms/g at the Cd 10,000 ppm in soil. This values is higher than every other we have seen in the reports for treatment with CdO. We are able to find out that the concentration of 10,000 ppm Cd in the form of CdO in the critical one towards rice plant. By contrast, such damage was not observed at even higher levels of ZnO and PbO were considered to have low toxicity toward rice plant. Also, a negative correlation between Zn or Cu accumulation in rice plants and Cd concentration in soil was found.     

Application of activated M/ZnO (M = Mn,Co, Ni,Cu, Ag) in photocatalytic degradation of diazo textile coloring dye

Activated ZnO powder has been prepared by procedures involving first its dissolution in nitric acid, then simultaneous treatment by adding NH₄OH and CO₂ bubbling leading to precipitation as Zn(OH)CO₃ (ZH) and further thermal decomposition of ZH at 400 °C. The gas evolution leads to formation of pores and increase in the specific surface area. Chemically activated M/ZnO powders doped with Mn, Co, Ni, Cu, and Ag have been obtained by the impregnation method. The samples have been characterized by ultraviolet-visible (UV-Vis) spectroscopy, diffuse reflectance (DR) UV-Vis, X-ray diffraction (XRD), single point Brunauer–Emmet–Teller (BET), scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS) methods. The experiments have shown that metal-doped activated ZnO powders possess higher photocatalytic activities in oxidative discoloration of model contaminant textile coloring dye Reactive Black 5 in slurry reactor compared to that of the pure ZnO. The XRD and XPS data have shown the presence of defects, nonstoichiometricity implying the formation of solid solutions. Copper-doped (1.5 wt%) activated ZnO (Cu²⁺ replaces Zn²⁺) is outstanding in its photocatalytic performance in discoloration of the dye due to the higher specific surface area and improved charge carrier separation.     

用光催化氧化法处理垃圾渗滤液的实验研究

以城市生活垃圾渗滤液作为研究对象 ,采用悬浮态半导体催化剂对渗滤液进行处理试验。研究了ZnO TiO2复合半导体催化剂的催化活性 ,并研究了各种实验条件、影响因素及处理效果。研究表明 ,在一定的试验条件下 ,用ZnO TiO2 复合半导体催化剂处理城市垃圾渗滤液效果较好 ,可作为垃圾渗滤液的深度处理。同时得到光催化氧化法处理渗滤液的最佳试验参数。     

Effects of realistic concentrations of TiO<Subscript>2</Subscript> and ZnO nanoparticles in <Emphasis Type="Italic">Prochilodus lineatus</Emphasis> juvenile fish

The impact of nanoparticles on fish health is still a matter of debate, since nanotechnology is quite recent. In this study, freshwater benthonic juvenile fish Prochilodus lineatus were exposed through water to three concentrations of TiO₂ (0.1, 1, and 10 μg l^?1) and ZnO (7, 70, and 700 μg l^?1) nanoparticles, as well as to a mixture of both (TiO₂ 1 μg l^?1?+?ZnO 70 μg l^?1) for 5 and 30 days. Nanoparticle characterization revealed an increase of aggregate size in the function of concentration, but suspensions were generally stable. Fish mortality was high at subchronic exposure to 70 and 700 μg l^?1 of ZnO. Nanoparticle exposure led to decreased acetylcholinesterase activity either in the muscle or in the brain, depending on particle composition (muscle—TiO₂ 10 μg l^?1; brain—ZnO 7 and 700 μg l^?1), and protein oxidative damage increased in the brain (ZnO 70 μg l^?1) and gills (ZnO 70 μg l^?1 and mixture) but not in the liver. Exposed fish had more frequent alterations in the liver (necrosis, vascular congestion, leukocyte infiltration, and basophilic foci) and gills (hyperplasia and epithelial damages, e.g., epithelial disorganization and epithelial loss) than the control fish. Thus, predicted concentrations of TiO₂ and ZnO nanoparticles caused detectable effects on P. lineatus that may have important consequences to fish health. But, these effects are much more subtle than those usually reported in the scientific literature for high concentrations or doses of metal nanoparticles.     

Heterogeneous photocatalytic oxidation of cyprodinil and fludioxonil in leaching water under solar irradiation

The efficiency of ZnO and TiO₂ suspensions in the photocatalytic degradation of two fungicides (cyprodinil and fludioxonil) in leaching water was investigated. The experiments were carried out at pilot plant scale using compound parabolic collectors under natural sunlight. The blank experiments for both irradiated compounds solutions showed that both oxides strongly enhanced the removal of the fungicides. The addition of an oxidant (Na₂S₂O₈) to the ZnO or TiO₂ increased the rate of photooxidation. The degradation of cyprodinil and fludioxonil followed first order kinetics according to the Langmuir-Hinshelwood model. Complete degradation of both fungicides was achieved within 4 h (t_30W = 18 min) when treated with illuminated ZnO. The disappearance time (DT₇₅), when referred to the normalized illumination time (t_30W), was lower than 40 and 550 min (t_30W = 2 and 40 min) for both fungicides using ZnO or TiO₂, respectively. ZnO appeared to be more effective in cyprodinil and fludioxonil oxidation than TiO₂ probably due to its nonstoichiometry.     

氧化锌法处理低浓度SO_2烟气的模拟实验研究

文中介绍了氧化锌法脱硫的基本原理,总结了国内外研究及应用现状,同时详细叙述了模拟实验采用的流程、主要仪器,着重分析了不同SO2浓度下的吸收率以及亚硫酸锌的氧化率与氧化时间、浆液温度的关系,提出了实验过程中发现的问题及可采取的措施,为后期中试以及工业化应用提供了设计依据。     

Semiconductor-assisted photodegradation of lignin, dye, and kraft effluent by Ag-doped ZnO

This work reports a preliminary study of semiconductor-assisted photochemical degradation of lignin, Remazol Brilliant Blue R and Kraft E1 paper effluent by using ZnO and Ag-doped ZnO photocatalysts. The doped semiconductor was prepared in the reaction media by photoreduction of silver nitrate. With the use of 100 mg of ZnO and 15 mg of Ag-ZnO, almost total decolorization of the dye and lignin samples in reaction times lower than 60 min were observed. Extending the photochemical reaction up to 120 min, the total organic carbon content (TOC) was reduced in 90%. For the paper effluent, a fast decolorization was obtained for relatively short reaction times. However, de TOC reduction was negligible (near of 10%) up to high reaction times (300 min). By using the Ag-ZnO photocatalyst, the toxicity of lignin and Kraft E1 effluent toward E. Coli was completely removed. For the dye, the formation of transient toxic species was observed.     

Comparison of azo dye degradation efficiency using UV/single semiconductor and UV/coupled semiconductor systems

This study examined degradation of azo dyes using photocatalytic oxidation (UV/semiconductor). The model substrates employed in this work were Procion Red MX-5B and Amaranth, while the photocatalysts were TiO2, ZnO, and SnO2. UV-Vis spectrum analysis demonstrated that the band gap energies of TiO2, ZnO, and SnO2 were 3.17, 2.92, and 4.13 eV, respectively. The band gap energy of SnO2 is insufficient to initiate photocatalytic reaction after UV irradiation (365 nm). The reaction rate constants fit a first-order reaction model and the reaction rate constant of Procion Red MX-5B for TiO2+SnO2 (0.31 h-1) is larger than that of TiO2 (0.24 h-1) and SnO2 at pH 10. The difference between the conduction bands of SnO2 and TiO2 enables the former to act as a sink for the photogenerated electrons. Most of the reaction rate constants had higher values at pH 10 than pH 7, and thus the OH attack could be assumed to represent the main reaction in this investigation. The quantities of sulfate and chloride ions released are below stoichiometry during the degradation. Owing to the sulfonate groups of Amaranth exceeding Procion Red MX-5B, Amaranth had larger electrostatic attraction than Procion Red MX-5B with the surface of ZnO, and also had higher adsorption percentage than Procion Red MX-5B on the surface of ZnO. The trend of adsorption is consistent with the reaction rate constant at pH 7, namely Amaranth>Procion Red MX-5B. The sulfate dissociation rate constant of Amaranth in UV/ZnO at pH 7 (0.49 h-1) approaches the overall rate constant (0.53 h-1); therefore, the first step involved in Amaranth can be suggested to the cleavage of the bonds of the C-S in Amaranth, causing sulfate ion formation.     

Evaluation of growth and biochemical indicators of Salvinia natans exposed to zinc oxide nanoparticles and zinc accumulation in plants

The adverse effects of zinc oxide nanoparticles (ZnO NPs) with an average diameter of 25 nm on the aquatic plant Salvinia natans (L.) All. were determined. Growth, superoxide dismutase (SOD) activity, catalase (CAT) activity, peroxidase activity, and chlorophyll content of the plants were measured after 7 days of exposure to different concentrations of ZnO NPs (1 to 50 mg L^?1). The particle distribution in the culture medium (without plants) during the first 24 h was determined using a Nanotrac 250 particle analyzer. We also investigated the zinc accumulation in leaves and roots of the plant after 7 days of exposure. Exposure to 50 mg L^?1 ZnO NPs significantly increased SOD and CAT activities (P?<?0.05) and significantly depressed photosynthetic pigments (P?<?0.05). However, plant growth was not significantly affected (P?>?0.05). NPs completely precipitated at the bottom of the container at 8 h except for the portions of dissolution and aggregation on the roots. ZnO NPs at a concentration of 50 mg L^?1 can adversely affect S. natans, and their stress is affected by their aggregation and dissolution.